Mixtures of epoxy cationic resins

ABSTRACT

A method for preparing an advanced epoxy cationic resin from an epoxy resin containing oxirane groups by converting at least some of the oxirane groups to cationic groups is improved by using as the epoxy-based resin a blend of (I) an epoxy resin obtained by reacting in the presence of a suitable catalyst (1) a diglycidylether of an aliphatic diol which diol is essentially free of ether oxygen atoms, such as a condensation product of 1,4-butanediol and epichlorohydrin, optionally (2) a diglycidylether of a dihydric phenol, for example a diglycidyl ether of bisphenol A, (3) a dihydric phenol such as bisphenol A, and optionally (4) a capping agent such as p-nonylphenol and (II) a different cationic epoxy resin. Such resin blends can be utilized in cathodic electrodeposition coating systems. Use of the diglycidylether of an aliphatic diol which diol is essentially free of ether oxygen atoms provides coating compositions with lower viscosity and produces deposition coatings of higher film build than compositions without this component.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 08/020,815 filedFeb. 22, 1993 (now U.S. Pat. No. 5,260,355), which is a division ofapplication Ser. No. 07/718,749 filed Jun. 21, 1991 (now U.S. Pat. No.5,206,274), which is a division of application Ser. No. 07/404,725 filedSep. 8, 1989 (now U.S. Pat. No. 5,064,880) which is a division ofapplication Ser. No. 07/069,475 filed Jul. 2, 1987 (now U.S. Pat. No.4,883,572).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention is concerned with the preparation of coating compositionsfrom epoxy-based resins and their application by cathodicelectrodeposition.

2. Description of the Prior Art

Electrodeposition has become an important method for the application ofcoatings over the last two decades and continues to grow in popularitybecause of its efficiency, uniformity and environmental acceptance.Cathodic electrodeposition has become dominant in areas where highlycorrosion-resistant coatings are required, such as in primers forautomobile bodies and parts. Epoxy based systems provide the bestoverall performance in this application and are widely used.

Cathodic electrodeposition resins based on conventional epoxies obtainedby reacting liquid diglycidyl ethers of bisphenol A with bisphenol A toproduce higher molecular weight epoxy resins have known disadvantages.Such products tend to have excessively high softening points resultingin poor flow out. In addition, such products require excessive amountsof solvent during their preparation. In order to improve flow, it hasbeen proposed to modify such conventional epoxy resins by reaction witha diol in the presence of a tertiary amine catalyst Thus, Bosso et al.,U.S. Pat. No. 3,839,252, describes modification with polypropyleneglycol. Marchetti et al., U.S. Pat. No. 3,947,339, teaches modificationwith polyesterdiols or polytetramethylene glycols. Wismer et al., U.S.Pat. No. 4,419,467, describes still another modification with diolsderived from cyclic polyols reacted with ethylene oxide. These variousmodifications, however, also have disadvantages. Tertiary amines orstrong bases are required to effect the reaction between the primaryalcohols and the epoxy groups involved. Since these reactions requirelong reaction times, they are subject to gellation because ofcompetitive polymerization of the epoxy groups by the base catalyst. Inaddition epoxy resins containing low levels of chlorine are required toprevent deactivation of this catalyst.

Many coating formulations applied by electrodeposition include pigmentsto provide color, opacity, application, or film properties Sturni et al.U.S. Pat. No. 3,936,405, describes pigment grinding vehicles especiallyuseful in preparing stable, aqueous pigment dispersions forwater-dispersible coating systems, particularly for application byelectrodeposition. The final electrodepositable compositions, asdescribed, contain the pigment dispersion and an ammonium or amine saltgroup solubilized cationic electrodepositable epoxy-containing vehicleresin and other ingredients typically used in electrodepositablecompositions. Among the kinds of resins used are various polyepoxidessuch as polyglycidyl ethers of polyphenols, polyglycidyl ethers ofpolyhydric alcohols and polyepoxides having oxyalkylene groups in theepoxy molecule.

Moriarity et al., U S. Pat. No. 4,432,850 discloses an aqueousdispersion of a blend of (A) an ungelled reaction product of apolyepoxide and a polyoxyalkylenepolyamine, which is then at leastpartially neutralized with acid to form cationic groups, and (B) anadditional cationic resin different from (A). The resulting dispersionis applied by cathodic electrodeposition and is disclosed as providinghigh throw power and films which are better appearing, more flexible andmore water-resistant.

Anderson et al. U.S. Pat. No. 4,575,523, discloses a film-forming resincomposition which when combined with a crosslinking agent andsolubilized, is capable of depositing high build coatings in cathodicelectrodeposition processes. The resin is a reaction product of amodified epoxy formed by reacting a water-soluble or water-misciblepolyol, an excess of polyamine, and an aliphatic monoepoxide.

The automobile industry still has needs in the areas of controlled filmthickness. The ability to build thicker, uniform films which are smoothand free of defects will allow the elimination of an intermediate layerof paint known as a primer surfacer or spray primer, previously requiredto yield a sufficiently smooth surface for the topcoat. Such anelimination results in removal of one paint cycle and provides moreefficient operations. Thicker electrocoat primers may also provideimproved corrosion resistance

SUMMARY OF THE INVENTION

The present invention is directed to a mixture of

I. an advanced epoxy-based cationic resin prepared by reacting in thepresence of a suitable catalyst

(A) a composition comprising (1) from about 20 to 100 weight percent ofa diglycidyl ether of an aliphatic diol which diol is essentially freeof ether oxygen atoms and (2) from zero to about 80 weight percent of adiglycidyl ether of a dihydric phenol with

(B) at least one dihydric phenol and optionally,

(C) a monofunctional capping agent wherein components (A) and (B) areemployed in such quantities that the resultant advanced epoxy resin hasan average epoxide equivalent weight of from about 350 to about 10,000,whereby there is formed an advanced epoxy resin having terminal oxiranegroups; and

subsequently converting at least some of the oxirane groups to cationicgroups and at least some of the oxirane groups to cationic groups and

II. a different epoxy-based cathodic electrodeposition resin.

The present invention is also directed to a coating compositioncomprising an aqueous dispersion of a mixture of the above-describedadvanced epoxy cationic resin with a different epoxy-based cathodicelectrodepositable resin and a method for coating such compositions.

Unexpectedly, incorporation of resins containing the advanced glycidylethers of aliphatic diols which diols are essentially free of etheroxygen atoms into the blends confer to cathodically electro-depositablecoating compositions produced therefrom the ability to build thickerfilms having controlled thickness during the electrodeposition process,as compared to a similar composition using an epoxy resin not containingthe aliphatic diol essentially free of ether oxygen atoms/glycidyl ethercomponent. The ability to deposit thicker films is highly desirable forreducing the number of paint applications required while improving thecorrosion resistance and appearance of the electrodeposited coating. Thefilm thickness can be controlled by adjusting the amount of thediglycidylether of an aliphatic diol which diol is essentially free ofether oxygen atoms incorporated into the epoxy resin. Generally,thickness increases with increasing content of this component.

Another advantage is that the blends of cationic epoxy resins containingthe diglycidylether of an aliphatic diol which diol is essentially freeof ether oxygen atoms have a lower viscosity at a given temperature thanunmodified cationic resins of the same molecular weight. This lowerviscosity allows the use of higher molecular weight resins and/or lesssolvent to achieve a viscosity comparable to an unmodified resin. Thelower viscosity cationic resins allow the coating composition greaterflowout during deposition and curing which results in better appearance.Alternatively, the lower viscosity cationic resins enable curing atlower temperatures to give equivalent flow and appearance. Finally,coatings produced using these epoxy resins have greater flexibility dueto incorporation of the diglycidylether of an aliphatic diol which diolis essentially free of ether oxygen atoms component as compared to thosebased on similar resins not containing that component.

All of the coating compositions of the invention provide usefulcathodically electrodepositable coatings having improved flowout, filmbuild, and flexibility properties due to the incorporation of the resincontaining the diglycidyl ether of an aliphatic diol which diol isessentially free of ether oxygen atoms as a component of the blend.

DETAILED DESCRIPTION OF THE INVENTION

The improvement of the present invention is provided by a blend of aselected advanced epoxy cationic resin with a different epoxy-basedcathodic electrodeposition resin.

The Advanced Epoxy Cationic Resin

The starting epoxy resin component for preparing the advanced epoxycationic resin required for the mixture of resins of this invention isan advanced resin prepared by reacting a composition comprising aglycidyl ether of an aliphatic diol which diol is essentially free ofether oxygen atoms (A-1) and optionally a glycidyl ether of a dihydricphenol (A-2) with a dihydric phenol (B) and optionally, a monohydriccapping agent (C). Glycidyl ethers of dihydric phenols useful for thepreparation of these resins are those having at least one, andpreferably an average of about two, vicinal epoxide groups per molecule.These polyepoxides can be produced by condensation of an epihalohydrinwith a polyphenol in the presence of a basic-acting substance.

Useful glycidyl ethers of polyphenols are represented by Formulae I andII: ##STR1## wherein A is a divalent hydrocarbon group having from 1 to12, preferably 1 to 6, carbon atoms; --S--, --S--S--, --SO--, --SO₂ --,--CO--, --O--CO--O--, --O-- or the like; each R is independentlyhydrogen or a hydrocarbyl group having from 1 to 3 carbon atoms; each R'is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group havingfrom 1 to 4 carbon atoms, or a halogen, preferably chlorine or bromine;n has a value from zero to 1; and n' has a value from zero to about 10,preferably from 0.1 to 5.

Polyphenols useful for the production of these polyepoxides include2,2-bis(4-hydroxyphenyl)propane (bisphenol A),1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane (bisphenolF), p,p'-hydroxybiphenol, resorcinol, hydroquinone, or the like. Theparticularly preferred polyglycidyl ethers of polyphenols are thediglycidyl ether of bisphenol A and the oligomeric polyglycidyl ethersof bisphenol A.

The glycidyl ethers of aliphatic diols essentially free of ether oxygenatoms useful in preparation of these epoxy resins include, for example,those represented by the following Formula III ##STR2## wherein each Ris independently hydrogen or a hydrocarbyl group having from 1 to 3carbon atoms; Z is a divalent aliphatic or cycloaliphatic groupessentially free of ether oxygen atoms and having from 2 to about 20,preferably from about 2 to about 12, carbon atoms or one of the groupsrepresented by the formulas ##STR3## A' is a divalent hydrocarbon grouphaving from 1 to about 6 carbon atoms; each R' is independentlyhydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 4carbon atoms; each R" is an aliphatic group having from 1 to about 6,preferably from 1 to about 4, carbon atoms: and n has a value of zeroor 1. Examples of useful aliphatic diols which are essentially free ofether oxygen atoms are 1,4-butanediol, 1,6-hexanediol,1,12-dodecanediol, neopentylglycol, dibromoneopentyl glycol,1,3-cyclohexanediol, hydrogenated bisphenol A,1,4-cyclohexanedimethanol, 1,2-cyclohexanediol, 1,4-cyclohexanediol,combinations thereof and the like.

The glycidyl ethers of aliphatic diols which are essentially free ofether oxygen atoms can be produced by the condensation of anepihalohydrin with an aliphatic diol which is essentially free of etheroxygen atoms having the structure:

    HO--Z--OH

where Z is as defined above. The resultant halohydrin ether product isthen dehydrohalogenated by known methods with a basic acting materialsuch as sodium hydroxide.

Some of the common methods of synthesis of the diglycidylethers ofaliphatic diols which diols are essentially free of ether oxygen atomsproduce significant amounts of organic chloride-containing impurities.However, other processes are known for preparing products with lowerlevels of such impurities. While the low-chloride resins are notrequired for the practice of this invention, they may be used, ifdesired, for possible improvements in the process of preparing theresins, in the storage properties of the resins or formulated coatingsmade therefrom or in the performance properties of the products.

The aliphatic epoxy resin or mixture thereof with an aromatic epoxyresin is reacted with a diphenol and, optionally, a capping agent toproduce epoxyfunctional resins having the desired epoxide (oxirane)group content which are used to prepare the cationic resins employed inthe invention. The effective proportions of the diglycidyl ethercomponents range from about 20 to 100, preferably from about 30 to 100weight percent of the diglycidylether of an aliphatic diol which diol isessentially free of ether oxygen atoms (A-1) and from about zero toabout 80 weight percent of the diglycidyl ether of a diphenol (A-2). Apreferred range is from about 30 to 100 weight percent of thediglycidylether of an aliphatic diol which diol is essentially free ofether oxygen atoms and correspondingly from zero to about 70 weightpercent of the diglycidyl ether of a phenol. The proportions of theglycidyl ether components (A=A-1 +A-2) and the dihydric phenol (B) areselected to provide an average epoxy equivalent weight in the advancedepoxy resin of from about 350 to about 10,000, preferably from about 600to about 3,000. Such proportions usually are in the range of from about60 to about 90 weight percent of A and from about 10 to about 40 weightpercent of B. Useful diphenolic compounds include those described aboveas suitable for production of polyepoxide. The preferred diphenol isbisphenol A. Also useful are the bisphenols produced by chain extensionof the diglycidyl ether of a bisphenol with a molar excess of abisphenol to produce a diphenolic functional oligomeric product.

The use of capping agents such as monofunctional phenolic compoundsprovides the advantageous ability to reduce the epoxide content of theresulting product without chain-extension reactions and thus allowsindependent control of the average molecular weight and the epoxidecontent of the resulting resin within certain limits. Use of amonofunctional compound to terminate a certain portion of the resinchain ends also reduces the average epoxy functionality of the reactionproduct. The monofunctional phenolic compound is typically used atlevels of zero to 0.7 equivalent of phenolic hydroxyl groups perequivalent of epoxy which would remain after reaction of substantiallyall of the phenolic groups of the diphenol.

Examples of useful monofunctional capping agents are monofunctionalphenolic compounds such as phenol, tertiary-butyl phenol, cresol,para-nonyl phenol, higher alkyl substituted phenols, and the like.Particularly preferred is para-nonyl phenol. The total number ofphenolic groups and the ratio of difunctional to monofunctional phenoliccompounds, if any are used, are chosen so that there will be astoichiometric excess of epoxide groups. Ratios are also chosen so thatthe resulting product will contain the desired concentration of terminalepoxy groups and the desired concentration of resin chain endsterminated by the monophenolic compound after substantially all of thephenolic groups are consumed by reaction with epoxy groups. Usually, theamount of the capping agent is from about 1 percent to about 15 percentbased on the total weight of the A and B components.

These amounts are dependent on the respective equivalent weights of thereactants and the relative amounts of the epoxy-functional componentsand may be calculated by methods known in the art. In the practice ofthis invention, the desired epoxide content of the reaction productuseful for preparation of the cationic resin is typically between 1 and5 percent, calculated as the weight percentage of oxirane groups, andpreferably is from about 2 to about 4 percent. These levels arepreferred because they provide, after conversion, the desired cationiccharge density in the resinous products useful in cathodicelectrodeposition These cationic resins are produced by conversion ofpart or all of the epoxy groups to cationic groups as described below.

Reaction of the monofunctional compound with epoxy groups of thepolyglycidylether components of the reaction mixture may be done priorto, substantially simultaneously with, or subsequent to thechain-extension reactions of the diphenolic compound and thepolyglycidylether components. The preferred method is to have all of thereactants present simultaneously.

Reactions of the above components to produce the epoxy resins aretypically conducted by mixing the components and heating, usually in thepresence of a suitable catalyst, to temperatures between 130° and 225°C., preferably between 150° and 200° C., until the desired epoxidecontent of the product is reached. The reaction optionally may beconducted in an appropriate solvent to reduce the viscosity, facilitatemixing and handling, and assist in controlling the heat of reaction.

Many useful catalysts for the desired reactions are known in the art.Examples of suitable catalysts include ethyltriphenylphosphonium acetateacetic acid complex, ethyltriphenylphosphonium chloride, bromide, iodideor phosphate, and tetrabutylphosphonium acetate. The catalysts aretypically used at levels of 0.01 to 0.5 mole percent of the epoxidegroups.

Appropriate solvents include aromatic solvents, glycol ethers, glycolether esters, high boiling esters or ketones, or mixtures. Other usefulsolvents will be apparent to those skilled in the art. Preferredsolvents are ethylene glycol monobutylether and propylene glycolmonophenylether. Solvent content may range from zero to about 30 percentof the reaction mixture. A solvent is usually chosen which is compatiblewith the subsequent cation-forming reactions and with the final coatingcomposition so that the solvent does not require subsequent removal.

The Nucleophile

The nucleophilic compounds which can be used advantageously in formingthe cations required by this invention are represented by the followingclasses of compounds, sometimes called Lewis bases:

(a) monobasic heteroaromatic nitrogen compounds;

(b) tetra (lower alkyl)thioureas;

(c) R¹ --S--R² wherein R¹ and R² individually are lower alkyl, hydroxylower alkyl or wherein R¹ and R² are combined as one alkylene radicalhaving 3 to 5 carbon atoms;

(d) ##STR4## wherein R³ and R⁴ individually are lower alkyl, hydroxylower alkyl, a ##STR5## group or R³ and R⁴ are combined as one alkyleneradical having from 3 to 5 carbon atoms, R⁶ is an alkylene group havingfrom 2 to 10 carbon atoms, R⁷ and R⁸ individually are lower alkyl and R⁵is hydrogen or lower alkyl, aralkyl or aryl, except that when R³ and R⁴together are an alkylene group then R⁵ is hydrogen, lower alkyl orhydroxyalkyl and when either or both of R³ and R⁴ is a ##STR6## radicalthen R⁵ is hydrogen; and (e) ##STR7## wherein R⁹, R¹⁰ and R¹¹individually are lower alkyl, hydroxy lower alkyl or aryl.

In this specification the term lower alkyl means an alkyl having from 1to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl,isobutyl, n-pentyl, isopentyl, n-hexyl and isohexyl

Representative specific nucleophilic compounds are pyridine,nicotinamide, quinoline, isoquinoline, tetramethyl thiourea, tetraethylthiourea, hydroxyethyl methyl sulfide, hydroxyethyl ethyl sulfide,dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, methyl-n-propylsulfide, methylbutyl sulfide, dibutyl sulfide, dihydroxyethyl sulfide,bis-hydroxybutyl sulfide, trimethylene sulfide, thiacyclohexane,tetrahydrothiophene, dimethylamine, diethylamine, dibutyl amine,N-methylethanolamine, diethanolamine and the ketimine derivatives ofpolyamines containing secondary and primary amino groups such as thoseproduced by the reaction of diethylene triamine orN-aminoethylpiperazine with acetone, methyl ethyl ketone ormethylisobutyl ketone; N-methylpiperidine, N-ethylpyrrolidine,N-hydroxyethylpyrrolidine, trimethylphosphine, triethylphosphine,tri-n-butylphosphine, trimethylamine, triethylamine, tri-n-propylamine,triisobutylamine, hydroxyethyldimethylamine, butyldimethylamine,trihydroxyethylamine, triphenylphosphine, andN,N,N-dimethylphenethylamine.

The Acid

Substantially any organic acid, especially a carboxylic acid, can beused in the conversion reaction to form onium salts so long as the acidis sufficiently strong to promote the reaction between the nucleophileand the vicinal epoxide group(s) on the resinous reactant. In the caseof the salts formed by addition of acid to a secondary amine/epoxy resinreaction product, the acid should be sufficiently strong to protonatethe resultant tertiary amine product to the extent desired.

Monobasic acids are normally preferred (H⊕A⊖). Suitable organic acidsinclude, for example, alkanoic acids having from 1 to 4 carbon atoms(e.g., acetic acid, propionic acid, etc.), alkenoic acids having up to 5carbon atoms (e g., acrylic acid, methacrylic acid, etc. )hydroxy-functional carboxylic acids (e.g., glycolic acid, lactic acid,etc.) and organic sulfonic acids (e.g., methanesulfonic acid), and thelike. Presently preferred acids are lower alkanoic acids of 1 to 4carbon atoms with lactic acid and acetic acid being most preferred. Theanion can be exchanged, of course, by conventional anion exchangetechniques. See, for example, U.S. Pat. No. 3,959,106 at column 19.Suitable anions are chloride, bromide, bisulfate, bicarbonate, nitrate,dihydrogen phosphate, lactate and alkanoates of 1-4 carbon atoms.Acetate and lactate are the most preferred anions.

The Conversion Process to Form Cationic Resins

The conversion reaction to cationic resins is normally conducted bymerely blending the reactants together and maintaining the reactionmixture at an elevated temperature until the reaction is complete orsubstantially complete. The progress of the reaction is easilymonitored. The reaction is normally conducted with stirring and isnormally conducted under an atmosphere of inert gas (e.g., nitrogen).Satisfactory reaction rates occur at temperatures of from about 25° C.to about 100° C., with preferred reaction rates being observed attemperatures from about 60° to about 80° C.

Good results can be achieved by using substantially stoichiometricamounts of reactants although a slight excess or deficiency of theepoxy-containing resin or the nucleophile can be used. With weak acids,useful ratios of the reactants range from 0.5 to 1.0 equivalent ofnucleophile per epoxide group of the resin and 0.6 to 1.1 equivalents ofacid per epoxide. These ratios, when combined with the preferred epoxidecontent resins described above, provide the desired range of cationiccharge density required to produce a stable dispersion of the coatingcomposition in water. With still weaker acids (e.g., a carboxylic acid,such as acetic acid) a slight excess of acid is preferred to maximizethe yield of onium salts. In preparing the compositions in which thecationic group being formed is an onium group, the acid should bepresent during the reaction of the nucleophile and the epoxy group ofthe resin. When the nucleophile is a secondary amine, the amine-epoxyreaction can be conducted first, followed by addition of the acid toform the salt and thus produce the cationic form of the resin.

For the onium-forming reactions, the amount of water that is alsoincluded in the reaction mixture can be varied to convenience so long asthere is sufficient acid and water present to stabilize the cationicsalt formed during the course of the reaction. Normally, it has beenfound preferable to include water in the reaction in amounts of fromabout 5 to about 3 moles per epoxy equivalent. When the nucleophile is asecondary amine, the water can be added before, during, or after theresin epoxy group/nucleophile reaction. The preferred range of chargedensity of the cationic, advanced epoxy resin is from about 0.2 to about0.6 milliequivalent of charge per gram of the resin.

It has also been found advantageous to include minor amounts ofwater-compatible organic solvents in the reaction mixture. The presenceof such solvents tends to facilitate contact of the reactants andthereby promote the reaction rate. In this sense, this particularreaction is not unlike many other chemical reactions and the use of suchsolvent modifiers is conventional. The skilled artisan will, therefore,be aware, of which organic solvents can be included. One class ofsolvents that we have found particularly beneficial are the monoalkylethers of the C₂ -C₄ alkylene glycols. This class of compounds includes,for example, the monomethyl ether of ethylene glycol, the monobutylether of ethylene glycol, etc. A variety of these alkyl ethers ofalkylene glycols are commercially available.

When a desired degree of reaction is reached, any excess nucleophile canbe removed by standard methods, e g., dialysis, vacuum stripping andsteam distillation.

The Other Resin

The other resin which is blended with the advanced epoxy cationic resincontaining the glycidyl ether of an aliphatic diol which diol isessentially free of ether oxygen atoms component is broadlycharacterized as a different cathodically electrodepositable resin.Preferred kinds of the different electrodepositable resins areepoxy-based resins, particularly those resins containing a reactedglycidyl ether of a dihydric phenol which has been advanced with adihydric phenol such as bisphenol A. Examples of these differentcathodically electrodepositable resins include resins like thosedescribed above except that they contain none, or less than the minimumamount, of the advanced glycidyl ether of an aliphatic diol which diolis essentially free of ether oxygen atoms. Conventional epoxy resinsobtained by reacting liquid diglycidyl ethers of bisphenol A withbisphenol A are among the more specific examples of the class of otherresins which can be a portion of the blend.

Several kinds of epoxy-based resins which may be used in the blends aredescribed in various patents as follows: Jerabek in U.S Pat. No.4,031,050 describes cationic electrodeposition resins which are thereaction products of an epoxy-based resin and primary or secondaryamines. Jerabek et al. U.S. Pat. No. 4,017,438 describes reactionproducts of epoxy-based resins and blocked primary amines Bosso et aldescribe in U.S. Pat. Nos. 3,962,165; 3,975,346; 4,001,101 and 4,101,486cationic electrodeposition resins which are reaction products of anepoxy-based resin and tertiary amines. Bosso et al in U.S. Pat. No.3,959,106 and DeBona in U.S. Pat. No. 3,793,278 describe cationicelectrodeposition resins which are epoxy-based resins having sulfoniumsalt groups. Wessling et al in U.S Pat. No. 4,383,073 describes cationicelectrodeposition resins which are epoxy-based resins havingcarbamoylpyridinium salt groups. Bosso et al. U.S. Pat. No. 4,419,467discusses epoxy-based resins reacted with primary, secondary andtertiary amine groups as well as quarternary ammonium groups and ternarysulfonium groups. Sommerfeld U.S Pat. No. 4,076,676 describes aqueousdispersions of epoxy-based cationic resins which are the reactionproducts of a terminally functional epoxy resin, a tertiary amine and anitrogen resin. Belanger U.S Pat. No. 4,134,864, describes reactionproducts of epoxy-based resins, polyamines and a capping agent. Stillother suitable resins for use in the blends of this invention aredescribed in the patents in the following list:

    ______________________________________                                        U.S. Pat. No.       Patentee                                                  ______________________________________                                        4,182,831           Hicks                                                     4,190,564           Tominaga et al                                            4,296,010           Tominaga                                                  4,335,028           Ting et al.                                               4,339,369           Hicks et al.                                              ______________________________________                                    

Preparing the Blends

The blends of the additive resin of the present invention containing theadvanced glycidyl ether of an aliphatic diol which diol is essentiallyfree of ether oxygen atoms and the other resin can be prepared in anyone of several ways.

To prepare the desired product in an aqueous dispersion can involve thefollowing steps:

1. preparing the non-cationic resin,

2. converting the non-cationic resin to a cationic resin,

3. converting the cationic resin to a water-in-oil dispersion of theresin, and

4. converting the water-in-oil dispersion to an oil-in-water dispersion.

The blending of the cationic advanced resin prepared from a diglycidylether of an aliphatic diol which diol is essentially free of etheroxygen atoms and the other resin can occur with the resins at the samestage after step 1, after step 2, after step 3 or after step 4. Thusresins of the two types may be blended (a) as non-cationic resins, (b)as cationic resins (c) as water-in-oil dispersions of the cationicresins or (d) as oil-in-water dispersions. Subsequent steps are thencarried out on the blended material (except for (d)), to form thedesired product as an aqueous dispersion. These aqueous dispersions maybe treated further as desired according to the discussion below in otherembodiments of this invention.

The blending of the resins generally involves only gentle mixing. Whenblending is done with the non-cationic resins or with the cationicresins which are not yet in aqueous dispersion, a solvent for the resinsoptionally may be used to facilitate the mixing.

The relative amounts of the additive resin of the present invention andthe other resin in the blend are advantageously such as to provide fromabout 10 percent to about 90 percent of the additive resin, based on thetotal weight of cationic resin in the blend.

Other Embodiments of the Invention

The blends of resins of this invention in the form of aqueousdispersions are useful as coating compositions, especially when appliedby electrodeposition. The coating compositions containing the blends ofthis invention as the sole resinous component are useful but it ispreferred to include crosslinking agents in the coating composition tofacilitate curing so that the coated films will be crosslinked andexhibit improved film properties. The most useful sites on the resin forcrosslinking reactions are the secondary hydroxyl groups along the resinbackbone. Materials suitable for use as crosslinking agents are thoseknown to react with hydroxyl groups and include blocked polyisocyanates;amine-aldehyde resins such as melamine-formaldehyde, urea-formaldehyde,benzoguanine-formaldehyde, and their alkylated analogs; andphenolaldehyde resins.

Particularly useful and preferred crosslinking agents are the blockedpolyisocyanates which, at elevated temperatures, deblock and formisocyanate groups which react with the hydroxyl groups of the resin tocrosslink the coating. Such crosslinkers are typically prepared byreaction of the polyisocyanate with a monofunctional active-hydrogencompound.

Examples of polyisocyanates suitable for preparation of the crosslinkingagent are described in Bosso, et al. U.S. Pat. No. 3,959,106 in Column15, lines 1-24, incorporated by reference herein. Also suitable areisocyanate-functional prepolymers derived from polyisocyanates andpolyols using excess isocyanate groups. Examples of suitable prepolymersare described by Bosso, et al., in U S. Pat. No. 3,959,106, Column 15,lines 25-57, incorporated herein by reference. In the preparation of theprepolymers, reactant functionality, equivalent ratios, and methods ofcontacting the reactants must be chosen in accordance withconsiderations known in the art to provide ungelled products having thedesired functionality and equivalent weight.

Examples of polyisocyanates are the isocyanurate trimer of hexamethylenediisocyanate, toluene diisocyanate, methylene diphenylene diisocyanate,isophorone diisocyanate, and a prepolymer from toluene diisocyanate andpolypropylene glycol and a prepolymer of toluene diisocyanate andtrimethylolpropane.

Suitable blocking agents include alcohols, phenols, oximes, lactams, andN,N-dialkylamides or esters of alpha-hydroxyl group containingcarboxylic acids. Examples of suitable blocking agents are described inBosso, et al. U.S Pat. No. 3,959,106, in Column 15, line 58, throughColumn 16, line 6, and in Moriarity U.S. Pat. No. 4,452,930.Particularly useful are the oximes of ketones, also known as ketoximes,due to their tendency to deblock at relatively lower temperatures andprovide a coating composition which can be cured at significantly lowertemperatures. The particularly preferred ketoxime is methyl ethylketoxime.

These cationic resins of the invention, when formulated with certainpreferred ketoxime-blocked polyisocyanates, provide coating compositionswhich cure at significantly lower temperatures than those of the priorart.

The blocked polyisocyanates are prepared by reacting equivalent amountsof the isocyanate and the blocking agent in an inert atmosphere such asnitrogen at temperatures between 25° to 100° C., preferably below 70° C.to control the exothermic reaction. Sufficient blocking agent is used sothat the product contains no residual, free isocyanate groups. A solventcompatible with the reactants, product, and the coating composition maybe used such as a ketone or an ester. A catalyst may also be employedsuch as dibutyl tin dilaurate.

The blocked polyisocyanate crosslinking agents are incorporated into thecoating composition at levels corresponding to from about 0.2 to about2.0 blocked isocyanate groups per hydroxyl group of the cationic resin.

A catalyst optionally may be included in the coating composition toprovide faster or more complete curing of the coating. Suitablecatalysts for the various classes of crosslinking agents are known tothose skilled in the art. For the coating compositions using the blockedpolyisocyanates as crosslinking agents, suitable catalysts includedibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide,stannous octanoate, and other urethane-forming catalysts known in theart. Amounts used typically range between 0.1 and 3 weight percent ofbinder solids.

Unpigmented coating compositions are prepared by mixing the cationicresin blend with the crosslinking agent and optionally any additivessuch as catalysts, solvents, surfactants, flow modifiers, defoamers, orother additives. This mixture is then dispersed in water by any of theknown methods. A particularly preferred method is the technique known asphase-inversion emulsification, wherein water is slowly added withagitation to the above mixture, usually at temperatures ranging fromambient to 90° C., until the phases invert to form an organicphase-in-water dispersion. The solids content of the aqueous dispersionis usually between 5 and 30 percent by weight and preferably between 10and 25 percent by weight for application by electrodeposition.

Pigmented coating compositions are prepared by adding a concentrateddispersion of pigments and extenders to the unpigmented coatingcompositions. This pigment dispersion is prepared by grinding thepigments together with a suitable pigment grinding vehicle in a suitablemill as known in the art.

Pigments and extenders known in the art are suitable for use in thesecoatings including pigments which increase the corrosion resistance ofthe coatings. Examples of useful pigments or extenders include titaniumdioxide, talc, clay, lead oxide, lead silicates, lead chromates, carbonblack, strontium chromate, and barium sulfate.

Pigment grinding vehicles are known in the art. A preferred pigmentgrinding vehicle for use in this invention consists of a water-solublecationic resinous product, water, and a minor amount of glycol ethersolvent. The cationic resinous product is prepared by reacting anepichlorohydrin/bisphenol. A condensation product having an epoxidegroup content of about 8 percent with a nucleophile, an acid, and waterin a similar fashion as described above for the cationic resins used inthe preferred embodiment of the invention. The water-soluble product maybe diluted with water to form a clear solution useful as a pigmentgrinding vehicle.

The pH and/or conductivity of the coating compositions may be adjustedto desired levels by the addition of compatible acids, bases, and/orelectrolytes known in the art. Other additives such as solvents,surfactants, defoamers, anti-oxidants, bactericides, etc. may also beadded to modify or optimize properties of the compositions or thecoating in accordance with practices known to those skilled in the art.

Although the coating compositions of the invention may be applied by anyconventional technique for aqueous coatings, they are particularlyuseful for application by cathodic electrodeposition, wherein thearticle to be coated is immersed in the coating composition and made thecathode, with a suitable anode in contact with the coating composition.When sufficient voltage is applied, a film of the coating deposits onthe cathode and adheres. Voltage may range from 10 to 1,000 volts,typically 50 to 500. The film thickness achieved generally increaseswith increasing voltage. In the case of the coating compositions of theinvention, thicker films are achieved by incorporation of the diglycidylether of an aliphatic diol which diol is essentially free of etheroxygen atoms into the epoxy resin used to produce the cationic resins ofthe invention. Also, control over the final thickness may be exercisedby adjusting the amount of that component used. Current is allowed toflow for between a few seconds to several minutes, typically twominutes, over which time the current usually decreases. Any electricallyconductive substrate may be coated in this fashion, especially metalssuch as steel and aluminum. Other aspects of the electrodepositionprocess, such as bath maintenance, are conventional. After deposition,the article is removed from the bath and typically rinsed with water toremove that coating composition which does not adhere.

The uncured coating film on the article is cured by heating at elevatedtemperatures, ranging from about 200° to about 400° F., for periods ofabout 1 to about 60 minutes.

EXAMPLES

In the following examples, various materials were used which arecharacterized as follows:

Epoxy Resin A is the diglycidyl ether of 1,4-butanediol having anepoxide equivalent weight (EEW) of 125 available from WilmingtonChemical Corp as HELOXY™ WC-67.

Epoxy Resin B is the diglycidyl ether of cyclohexanedimethanol having an(EEW) of 163 available from Wilmington Chemical Corp as HELOXY™ MK-107.

Epoxy Resin C is the diglycidyl ether of neopentyl glycol having an EEWof 135 available from Wilmington Chemical Corporation as HELOXY™ WC-68.

Epoxy Resin D is a diglycidyl ether of bisphenol A having an EEW of 187.

CURING AGENT A

A one-liter, round-bottom flask equipped with a nitrogen inlet,thermometer, condenser, mechanical stirrer, and an addition funnel ischarged 626.3 parts of Spencer Kellog's SPENKEL P49-A6-60 (a 60 wt. %solution of an isocyanate terminated prepolymer prepared from toluenedisocyanate and trimethylolpropane dissolved in methoxypropyl acetate).The solution is stirred at ambient temperature (22° C. to 24° C.) and0.62 parts by weight of dibutyl tin dilaurate catalyst is added. Twohundred parts of 2-ethylhexanol is added dropwise over a period of 2hours. The temperature of the reaction mixture is allowed to rise to 50°C. to 60° C. during the addition. The reaction mixture is then cooled toambient temperature over a 2 hour period. The infrared spectrum of theproduct shows no residual unreacted isocyanate groups. The productsolution is approximately 68.9 percent nonvolatiles by weight.

CURING AGENT B

To a 2-liter reactor is added 523.1 grams of toluene diisocyanate. Whilestirring under nitrogen, 390 grams of 2-ethylhexanol is added dropwiseat a temperature between 22° C. and 32° C. An ice bath is used to coolthe reaction mixture. Upon completion of the addition, the ice bath isremoved and the mixture is allowed to reach 32° C. over a 30 minuteperiod. This mixture is heated to 60° C. and 206.1 grams of methylisobutyl ketone is added at once. Then, 134.0 grams oftrimethylolpropane is added over a ten minute period while heating thereaction mixture at 60° C. Then, 0.2 grams of dibutyl tin dilaurate isadded and the reaction is allowed to exotherm to 95° C. after which itis heated to 120° C. over a 50 minute period. Heating at 120° C. iscontinued for an additional 40 minutes. The reaction mixture is allowedto cool to 60° C. and then diluted with 197.1 grams of methyl isobutylketone and 44.8 grams of butanol. The product contains 70 percent solids(non-volatiles). Infrared spectroscopy shows no unreacted isocyanate ispresent.

PIGMENT GRINDING VEHICLE

The pigment grinding vehicle is prepared by charging into a two-liter,round-bottom flask fitted with a nitrogen inlet, thermometer, mechanicalstirrer and condenser 340.3 parts by weight (pbw) of Epoxy Resin D and109.7 pbw of bisphenol A. The mixture is stirred under a nitrogenatmosphere and heated to 90° C. to form a clear mixture. A solutioncontaining 70 percent by weight of ethyl triphenyl phosphonium acetateacetic acid complex in methanol (0.6 pbw) is added. The mixture is thenheated to 150° C. at a rate of 1° C. to 2° C. per minute and thenallowed to exotherm to 170° C. The temperature is raised to 175° C. andmaintained for 30 minutes, at which time the epoxide content of theresin is 8.1 percent by weight. The resin is cooled to 130° C., dilutedwith 50.0 pbw of ethylene glycol monobutyl ether, and cooled to 65° C.to give an epoxy resin solution. To 422 pbw of this epoxy resin solutionis added 47.1 pbw of N-methylethanolamine dropwise over a period of 22minutes with cooling to maintain the temperature at 65° C. to 74° C. Thetemperature is then maintained at 80° C. for 3 hours. A solution (75.4pbw) which contains 75 percent lactic acid is diluted with water (100pbw) and then the resulting solution is added at 75° C. to 80° C. to thereaction mixture at 75° C. to 80° C. Thereafter, dilution of the productwith additional water (458.7 pbw) provides a cationic resin solutioncontaining 40 percent non-volatiles.

PIGMENT PASTE A

A concentrated pigment paste is prepared by placing a pigment blend (100pbw) comprising 35 pbw of clay, 35 pbw of titanium dioxide, 20 pbw oflead silicate, and 10 pbw of carbon black in a metal paint can alongwith 50 pbw of Pigment Grinding Vehicle. Enough chrome-plated steelpellets (about 2 mm in diameter×5 mm long) are added to comprise aboutone-third of the final bulk volume. The pigments are ground anddispersed in the vehicle by placing the can on a paint shaker for 45minutes. Water is then added and blended in to reduce the viscosityslightly and the grinding pellets are removed by filtration. The finalpigment dispersion contains 55 percent pigment by weight.

PIGMENT PASTE B

Pigment Paste B is a pigment paste obtained from PPG Industries, Inc.designated Cationic Paste E 5410.

COATING AND TESTING THE COMPOSITIONS

The coating compositions are placed in a stainless steel tank, agitated,and maintained at 80° F. Unpolished steel test panels having Bonderite™40 treatment and P60 rinse available from Advanced Coating Technologies,Inc. are immersed in the tank and connected as the cathode to a D.C.voltage source, with the tank walls serving as the anode. The desiredvoltage is applied for two minutes, then the panels are removed, rinsedwith deionized water, and baked at 350° F. for 30 minutes

EXAMPLE 1

A cationic electrodeposition resin is prepared by charging into asuitable reactor 110 grams of Epoxy Resin A and 90 grams of Bisphenol A.The mixture is heated to 80° C. and 0.11 gram of ethyltriphenylphosphonium acetate acetic acid complex blended with 0.05 gram ofmethanol is added. This blend is stirred while heating at 1.5° C./min.to 150° C. whereupon it exotherms to 165° C. where the temperature isheld for about one hour. The epoxy equivalent weight (EEW) of theresulting resin is 1654 grams/equivalent.

After cooling this resin to 120° C., 22 grams of propylene glycol phenylether solvent is added. The resin solution is cooled to 60° C. and 9grams of N-methylethanolamine is added whereupon it exotherms to 67° C.and the temperature is controlled at 80° C. for one hour.

To the reaction product at 60° C., are added 3.29 grams of dibutyl tindilaurate catalyst and 159.5 grams of Curing Agent A.

While agitating continuously, a cationic dispersion is prepared byadding to the resulting mixture, at 60° C., 12.3 grams of an aqueoussolution containing 72.5 percent by weight of lactic acid which isfollowed by the slow addition of 1446 grams of deionized water. Thisproduct is referred to as Resin Dispersion 1.

Resin Dispersion 1 is blended with 123 grams of Pigment Paste A to yielda pigmented cathodic electrodeposition paint having a pigment to binderratio of 0.2 to 1.

The above prepared pigmented cationic electrodeposition paint is blendedwith various amounts of a commercial cathodic electrodeposition primer,ED 3002 available from PPG Industries, Inc. Cationic electrodepositionbaths are prepared by adding zero, 10, 20, 25 and 30 weight percent ofthe above described pigmented dispersion to the ED 3002. Filmthicknesses are given in Table I.

                  TABLE I                                                         ______________________________________                                        ELECTRODEPOSITED FILMS                                                        Film Thickness in mils at the indicated voltage.                              PIGMENTED                                                                     RESIN                                                                         DISPERSION                                                                              ED 3002    200      250     300                                     PERCENT   PERCENT    VOLTS    VOLTS   VOLTS                                   ______________________________________                                         0*       100        0.45     0.57    0.64                                    10        90         0.64     0.85    2.1                                     20        80         0.78     1.1     2.4                                     25        75         0.87     1.3     2.6                                     30        70         0.99     1.7     2.8                                     ______________________________________                                         *Not an example of the invention.                                        

The above data shows that film thicknesses can be controlled by blendingdifferent proportions of the described critical cationicelectrodeposition dispersion with a commercial cathodicelectrodeposition paint and applying the resulting paint at a selecteddeposition voltage.

EXAMPLE 2

A cationic electrodeposition resin is prepared by charging into asuitable reactor 630 grams of Epoxy Resin B and 370 grams of BisphenolA. The mixture is heated to 80° C. and 0.63 gram of ethyltriphenylphosphonium acetate acetic acid complex blended with 0.27 gram ofmethanol is added. This blend is stirred while heating at 1.5° C./min.to 150° C. whereupon it exotherms to 165° C. where the temperature isheld for about one hour. The epoxy equivalent weight (EEW) of theresulting resin is 1453 grams/equivalent.

After cooling, 175 grams of this advanced epoxy resin to 120° C., 20.4grams of propylene glycol phenyl ether solvent is added. The resinsolution is cooled to 60° C. and 9 grams of N-methylethanolamine isadded whereupon it exotherms to 67° C. and the temperature is controlledat 80° C. for one hour.

To the reaction product at 60° C., are added 1.84 grams of dibutyl tindilaurate catalyst and 131.4 grams of Curing Agent B.

While agitating continuously, a cationic dispersion is prepared byadding to the resulting mixture, at 60° C., 103 grams of an aqueoussolution containing 72.5 percent by weight of lactic acid which isfollowed by the slow addition of 1237 grams of deionized water. Thisproduct is Resin Dispersion 2.

Resin Dispersion 2 from above is blended with Pigment Paste A to yield apigmented cathodic electrodeposition paint having a pigment to binderratio of 0.2 to 1.

The above prepared pigmented cationic electrodeposition paint is blendedwith various amounts of a commercial cathodic electrodeposition primer,ED 3002 available from PPG Industries, Inc. Cationic electrodepositionbaths are prepared by adding zero, 10, 20, 25 and 30 weight percent ofthe above described pigmented dispersion to the ED 3002.

Steel panels pretreated with zinc phosphate are cathodicallyelectrodeposited (coated) at various voltages for 2 minutes at a bathtemperature of 80° F. (27° C.). The wet films are baked at 350° F. (176°C.) for 30 minutes. Film thicknesses are given in Table II.

                  TABLE II                                                        ______________________________________                                        ELECTRODEPOSITED FILMS                                                        Film Thickness in mils at the indicated voltage.                              PIGMENTED                                                                     RESIN                                                                         DISPERSION                                                                              ED 3002    200      250     300                                     PERCENT   PERCENT    VOLTS    VOLTS   VOLTS                                   ______________________________________                                         0*       100        0.45     0.57    0.64                                    10        90         0.52     0.67    0.75                                    20        80         0.59     0.71    0.78                                    25        75         0.62     0.75    0.92                                    30        70         0.67     0.79    0.98                                    ______________________________________                                         *Not an example of the invention.                                        

The above data shows that the film thickness can be controlled byblending different proportions of the described cationicelectrodeposition dispersion with a commercial cathodicelectrodeposition paint and applying the resulting paint at a selecteddeposition voltage.

EXAMPLE 3

A cationic electrodeposition resin is prepared by charging into asuitable reactor 464 grams of Epoxy Resin C and 336 grams of BisphenolA. The mixture is heated to 80° C. and 0.46 gram of ethyltriphenylphosphonium acetate acetic acid complex blended with 0.20 gram ofmethanol is added. This blend is stirred while heating at 1.5° C./min.to 150° C. whereupon it exotherms to 165° C. where the temperature isheld for about one hour. The epoxy equivalent weight (EEW) of theresulting resin is 1830 grams/equivalent.

After cooling 175 grams of this advanced epoxy resin to 120° C., 19.4grams of propylene glycol phenyl ether solvent is added. The resinsolution is cooled to 60° C. and 7.5 grams of N-methylethanolamine isadded whereupon it exotherms to 67° C. and the temperature is controlledat 80° C. for one hour.

To the reaction product at 60° C., are added 1.82 grams of dibutyl tindilaurate catalyst and 130.4 grams of Curing Agent B.

While agitating continuously, a cationic dispersion is prepared byadding to the resulting mixture, at 60° C., 8.57 grams of an aqueoussolution containing 72.5 percent by weight of lactic acid which isfollowed by the slow addition of 1223 grams of deionized water. Thisproduct is Resin Dispersion 3.

The Resin Dispersion from above is blended with the Pigment Paste B toyield a pigmented cathodic electrodeposition paint having a pigment tobinder ratio of 0.2 to 1.

The above prepared pigmented cationic electrodeposition paint is blendedwith various amounts of a commercial cathode electrodeposition primer,ED 3002 available from PPG Industries, Inc. Cationic electrodepositionbaths are prepared by adding zero, 10, 20, 25 and 30 weight percent ofthe above described pigmented dispersion to the ED 3002.

Steel panels pretreated with zinc phosphate are cathodicallyelectrodeposited (coated) at various voltages for 2 minutes at a bathtemperature of 80° F. (27° C.). The wet films are baked at 350° F. (176°C.) for 30 minutes. Film thicknesses are given in Table III.

                  TABLE III                                                       ______________________________________                                        ELECTRODEPOSITED FILMS                                                        Film Thickness in mils at the indicated voltage.                              PIGMENTED                                                                     RESIN                                                                         DISPERSION                                                                              ED 3002    200      250     300                                     PERCENT   PERCENT    VOLTS    VOLTS   VOLTS                                   ______________________________________                                         0*       100        --       0.35    0.40                                    10        90         0.30     0.36    0.47                                    20        80         0.37     0.42    0.50                                    25        75         0.40     0.46    0.56                                    30        70         0.43     0.54    0.63                                    ______________________________________                                         *Not an example of the invention.                                        

The above data shows that the film thickness can be controlled byblending different proportions of the described cationicelectrodeposition dispersion with a commercial cathodicelectrodeposition paint and applying the resulting paint at a selecteddeposition voltage.

What is claimed is:
 1. A mixture ofI. an advanced epoxy cationic resinprepared by reacting in the presence of a suitable catalyst(A) acomposition comprising (1) from about 20 to 100 weight percent of adiglycidyl ether of an aliphatic diol which diol is essentially free ofether oxygen atoms and (2) from zero to about 80 weight percent of adiglycidyl ether of a dihydric phenol with (B) at least one dihydricphenol and optionally, (C) a monofunctional capping agent: whereincomponents (A) and (B) are employed in such quantities that theresultant advanced epoxy resin has an average epoxide equivalent weightof from about 350 to about 10,000, whereby there is formed an advancedepoxy resin having terminal oxirane groups; and subsequently convertingat least some of the oxirane groups to cationic groups and II. adifferent epoxy cathodic electrodeposition resin.
 2. The mixture ofclaim 1 in which the amount of diglycidylether of an aliphatic diolessentially free of ether oxygen atoms is from about 30 weight percentto 100 weight percent.
 3. The mixture of claim 2 in whichthediglycidylether of an aliphatic diol essentially free of ether oxygenatoms (A) (1) is represented by the following Formula III ##STR8##wherein each R is independently hydrogen or a hydrocarbyl group havingfrom 1 to 3 carbon atoms; Z is one of the groups represented by theformulas ##STR9## or an aliphatic or cycloaliphatic group having from 2to about 20 carbon atoms other than groups (i) or (ii); A' is a divalenthydrocarbon group having from 1 to about 6 carbon atoms; each R' isindependently hydrogen, a hydrocarbyl or hydrocarbyloxy group havingfrom 1 to 4 carbon atoms; each R" is an aliphatic group having from 1 toabout 6 carbon atoms; and n has a value of zero or 1; the diglycidylether of a dihydric phenol (A) (2) represented by the following FormulasI or II or a combination thereof ##STR10## wherein each A isindependently a divalent hydrocarbon group having from 1 to 12 carbonatoms, --S--, --S--S--, --SO--, --SO₂ --, --CO--, --O--CO--O-- or --O--;each R is independently hydrogen or a hydrocarbyl group having from 1 to3 carbon atoms; each R' is independently hydrogen, a hydrocarbyl orhydrocarbyloxy group having from 1 to about 4 carbon atoms; n has avalue from zero to 1; and n' has a value from zero to
 10. 4. The mixtureof claim 3 in which the epoxide equivalent weight of the advanced epoxyresin is from about 600 to about 3,000.
 5. The mixture of claim 4wherein the diglycidyl ether of a dihydric phenol (A) (2) is representedby Formula II wherein each R is hydrogen, A is an isopropylidene groupand n is zero.